Catalyst recovery



May 9, 1944. J. M. PAGE, JR cATALYsT RECOVERY Filed Nov. 3o, 1940 MWL M Mh. 4

e ,m fk ILM .Aluminum chloride has been used, asa catalyst to promote the cracking .oi hydro- Patenleil May' 9,

t CATALYST RECOVERY James M. Page.

ration o! Indiana r r Jr., Chicago, Ill., miglior to Standard Oil Company, Chica:

o, lll., a corpov Application November so, 1940, serial Nc. 368,003 1 claims. (ol. iss-ss) This invention relates to the recovery of aluminum halide catalystsv and relates more particlarly to the reactivation oi aluminum halide catalysts degraded during the conversion 'of hydrocarbons.

The use of aluminum halide catalysts for the conversion of hydrocarbons, either -alone or in the presence of suchadded promoters as hydrogen halides, organic halides, etc., is well known. for exsmple,

carbons, particularly high molecular yweight hydrocarbons such as those found in kerosene, gas oils, etc.; olens to form higher molecular weight oleilns of gasoline or lubricating oil boiling range; vthe alkylation of isoparamnic oraromatic hydrocarbons with olenic .hydrocarbons throughout a wide boiling range; the isomerization of straightchain hydrocarbons to branched-chain hydrocarbons; and numerous additional conversion processes wherein hydrocarbons or mixtures of hydrocarbons, particularly those of petroleum origin are converted to other hydrocarbons of commercially more desirable characteristics as regards configuration, boiling range, octane number, oxidation stability, etc.

Inpractically all of these processes the aluminum halide which originally was granular and dry is gradually vconverted to a sludge-like mass,

passing through various stages from a pale col-- ored, thin oil to highly resinous black, tarry or at times coky material. The actual mechanism of this conversion is not understood but apparently the catalyst forms complex compounds with4 the hydrocarbon undergoing treatment, thecomplexes building up as the treatment continues orV as the severity of the conditions is increased.y

Generallyspeaking, the hydrocarbon portion of the complex is highly unsaturated but the exact chemical structure dees accurate analysis. Throughout this specification and the claims the term aluminum halide-hydrocarbon sludge is intended to designate the metal halide-organic complex formed by the reaction of analuminum halide with a hydrocarbon orhydrocarbon mixture.

,It has been established that fresh 'aluminum chloride or aluminum bromide is .extremely active as a catalyst and that when used for the conversion of hydrocarbons it often carries the reactions to extremes and introduces undesirable sidereactions which cannot be controlled. Such violent activity is not too deleterious in such conversion processes as catalytic cracking but in the polymerization of normally gaseous l the catalytic activity of those reactions where a milder catalytic action is required, such as' alkylation. isomerization and polymerization processes, it is desirable to modify the aluminum halide catalyst. It has been discovered that in the light red oil complexes; which are quite mobile and fluid, the catalytic activity of the aluminum halide is suiiiciently modified or masked to be acceptable as a catalyst but still retains sumcient activity to promote the desired hydrocarbon conversion. These red oil complexes are apparentlyV the result of the interaction'iof aluminum halideand hydrocarbons and while their actual composition, as stated before, cannot be definitely determined, generally speaking, they contain from about 10 .to about hydrocarbons attached to the aluminum halide.

Many methods have been suggested for the recovery of aluminum halide from an aluminum halide sludge. Suchmethods include distillation, coking, destructive hydrogenation of the hydrocarbon complex to yield aluminum halides and hydrocarbons, decomposition of the aluminum halide to aluminum oxide and a halogen, etc. In all such methods the primary object is to recover the aluminum halide free of the hydrocarbons with which it formed a complex material and to obtain the substantially pure metal halide.

It is an object of my invention to provide a process for the reactivation of aluminum halidehydrocarbon sludge. Another object of my invention is to provide a process for the restoration of catalytic activity to an aluminum halide catalyst spent as regards hydrocarbon conversion, A further object of this invention'is to provide a process for the recovery of active catalytic material from an aluminum halide-hydrocarbon sludge. My invention also has as anadditional object the provision of a process for regenerating a spent aluminum' halide catalyst to a point wherein it may be reused in the conversion of hydrocarbon material. Additional objects and advantageswill become apparent as the description oi y invention proceeds, read in conjunction wit the accompanying drawing which forms a part of this specification andwhich is a simple flow diagram of one form of apparatus suitable for carrying out an embodiment of my process.

Briefly stated,'I have Vfoundthat the catalytic activity o'f an aluminum s halide-hydrocarbon sludge can be substantially restored by contacting it with hydrogen in the presence of a hydrogenation catalyst under conditions of temperature and pressure which promote the reactivation. It should be stated emphatically that my is applicable to the restoration of spent aluminum halide catalyst from any hydrocarbon conversion material available substantially or entirely hydrocarbons process, it is particularly suitable for the recovery:-`

of catalyst suitable for use in such processes as alkylation, isomerization, etc., modiiled or milder catalyst than the purealuminum halide.

Referring now to the drawing, an active aluminum halide-hydrocarbon complex is withdrawn from catalyst storage opening valve I2 therein and directed toreactor I3.v Feed stock enters from line I twhich Joins line I I and commingles with the catalyst. As feed stock I can employ any suitable hydrocarbon or hydrocarbon mixture which it may be desirable to convert to more valuable products. For example; the feed stock can befnormally gaseous and/or liquid hydrocarbons comprising essentially straight-chain or only slightly branched-chain paraflins which can bel isomerized to a highly branched conguration under the proper operat ing conditions; the feed stock can also be a mixture of oleiinic and paraillnicv hydrocarbonsliquid or gaseous, and containing a substantial amount of isoparailnic hydrocarbons therein, which is suitable for an alkylation reaction; or the feed stock can be predominantly oleiinic in character, for polymerization to hydrocarbons of higher molecular weight. Broadly speaking, I prefer to employ aromatic-free feed stocks, since aromatic hydrocarbons appear to degrade the catalyst and ly than do naphthenic or aliphatic hydrocarbons.

The feed stock can include with the hydrocarbon materials any promoters to be used in facilitating the reaction. Many of the reactions employing aluminum halides, and particularly aluminum halide-hydrocarbon complexes as a catalyst, are desirably carried out in the presence of a hydrogen halide, such as hydrogen chloride or hydrogen bromide, or in the presence of a compound yielding a hydrogen halide under the conditions of operation, such as organic halides, etc.v These compounds apparently promote the ease or smoothness with which the reaction will progress, and are suitably included with the feed stock, or they can be addedseparately, by means not shown. Hydrogen is often added during conversion processes involving aluminum halide-type catalysts, and this can also be included with the feed stock at the desired pressure, or can be added separately by means not shown.

Pump I5 in line Il and pump I6 inline I4 aid in commingling the catal st and feed and directing it to reactor I3. A mixing device can be inserted at the juncture of the two lines if desired..

As shown, reactor I3 has atubular coil Il within a vessel I8, which can be maintained at any desired temperature. The turbulent iiow through the coil serves to keep the reactants thoroughly intermingled, assuring intimate contact, andthe time fof contact can be controlled both by the rate of ilow and the length of coil employed. Such f afreactor is equally applicable to ,alkylatiom isomeriz'tatlon orA polymerization reactions. Other suitable' reactors can be substituted, however,

Which require' a (not shown) without departing from the scope of my invention, and can include such means as a Jacketed vessel with mechanical stirrers, jet injectors, oriilce mixers, etc., or a packed tower: in fact any means for insuring intimate contact between the reactants and for maintaining a desired temperature canbe employed. v 4 ,q

VY.('Jor'iverted hydrocarbons..K unconverted feed stock'arl'd catalyst pasgfrom reactor I3 via line L9 to separator 20 wherein the catalyst and the are settled and separated. the hydrocarbong being withdrawn overhead through linev 2| 'and directed to a fractionation system for recoveryof desired products, and recycle, yif desired; of unconverted feed stock.

'I'he`.'catalyst"is withdrawn from separator 20 i: -throughjline 22 controlled by valve 23. In some tank I0 through line II by reduce its activity much more rapidinstances the catalyst is only partially spent during thecourse of the reaction, and therefore it cankbe recycled to the reactor by opening valve 2l in line 25vwhich joins line II, where it can replace in whole orin partvthe fresh catalyst from storage tank I 0. Eventually, however, the catalyst becomes so viscous and heavy that it is no longer effective for promoting the conversion of hydrocarbons and, accordingly, the spent catalyst is directed from line 22 to a regeneration system byl opening valve 26 in line 21. Hydrogen is introduced from an outside source (not shown) via line 28, and can be mixed catalyst by opening valve 29 in line 30 which Joins line 21, or it can be added to the regeneration reactor separately by opening valve 3| in line 32. The regeneration is carried out at pressures within the range of fromabout 40 to about 400 atmospheres, which pressure can be supplied by pump 21a and compressor 34 in lines 2'I and 2l, respectively.

The aluminum halide-hydrocarbon sludge and hydrogen are heated to temperatures within the range of from about 200 F. to about 500 F., de pending to a large extent upon the hydrogenation catalyst employed, and accordingly pass through heater 35. In the event that the catalyst sludge and hydrogen are injected separately into the regeneration reactor, means for heating each stream must be provided. If desired, hydrogen chloride can be added to suppress any tendency toward aluminum or aluminum oxide formation, and can be added through line 33.

Regeneration reactor 36 comprises a drum 31. the interior of which is lled with catalytic material 38 which can be packed into the drum in any suitable manner, as for example in small lumps or on trays 3,9, as illustrated. As catalysts I can employ any suitable hydrogenation catalyst,1 such as the oxides or sulfldes of the heavy solid metals of the sixth group of their mixtures with each other or with other compounds, such as alumina, magnesia, zinc oxide, aluminum sulde, etc. I particularly prefer a rugged type catalyst, of which molybdenum suliide is an excellent example. In place of a regeneration reactor of the type described, I can add the hydrogenation catalyst directly to the sludge stream (by means not shown) together with the hydrogen and any hydrogen chloride used. In this event, vessel 3'I becomes a soaking drum" or other means for obtaining the desired contact time, orcan be a pipestill or other reactor in which the regeneration takes place. The hydrogenation catalyst can be left suspended in the regenerated aluminum halide complex catalyst, or can be removedtherefrom after regeneration by known means for removing solids from liquids.

directly with the spent.

the periodic table,

or other well-` inthe hydrocarbon conversion. lif the catalyst has been used to such an extent 4acquired high density or an initial hydrogen pressure The catalyst sludge and hydrogen which is substantially all inthe liquid phase pass upward through the catalyst bed, the contact time varying, for example, from about three hours to six hours, depending to a large degree upon the extent of degradation of the aluminum halide catalyst and the other conditions employed. The unused hydrogen, which should be present in considerable excess, passes overhead through line 4|, together with any light hydrocarbons, such as methane and ethane which may have been i'ormed during the regeneration. The gaseous fraction is cooled in cooler 4|, and directed to flash drum 42, in which the hydrogen is separated from the hydrocarbon material. A pressure-reducing valve 40a can be inserted in line 40 prior to drum 42. The light hydrocarbons are withdrawn through line 43, while the hydrogen passes out through line 44and can be withdrawn for use elsewhere by opening valve 45 in line 46 but preferably is recycled to the regeneration step by opening valve 41 in line 48 which joins line 28.

y Regenerated catalyst plusy normally liquid hydrocarbons formed during the reaction pass from regenerator 35 via line 49 to .separator 50, the hydrocarbons passing overhead therefrom through line while the regenerated catalyst is withdrawn through line 52. The regenerated aluminum halide-hydrocarbon complex, in a fluid, mobile state, can be withdrawn for use in any other process or for separate storage by opening valve 53 in line 54, but preferably is returned to storage tank l0 for further use in reactor I3 by opening valve 55 in line 56.

The exact temperature used for regeneration will depend to vsome extent upon the degree of use to which the catalyst has been subjected In other words,

that it is substantially completely exhausted so far as catalytic activity has even become resinous or tarry inappearance, then more extreme conditions as well as longerperiods of reactivation must necessarily be employed. 0n the other hand, if -the catalyst is to be subjected to reactivation when it has fallen below a certain opti` mum conversion constant, then milder conditions and shorter times ot reactivation are suitable. If the sludge is it can be thinned or diluted with mobile, thin sludge suitably held in separate storage for this purpose. y

As a specific example of my process, a light aromatic-free naphtha feed is treated with a fresh aluminum chloride-hydrocarbon complex for a period of iifteen hours at a temperature of about 330 F. for the isomerlzation of straightchain parailins to isoparaillns. At the end of this period the catalytic activity issuillciently diminished so that the catalyst is no longer effective for promoting the reaction. The spent catalyst is then-passed with hydrogen over a molybdenum sulfide catalyst held on trays, using of about 350 atmos- A temperature of about 450 F. is emleast as high a temperature as pheres. ployed, or at possible without coking or crackingthe complel, and a contact regenerated .active uid catalyst can now be returned to the isomerlzation reaction for the further conversion of the light naphtha feed.

By the use of hydrogen the aluminum halide'- hydrocarbon sludge can be restored to lan active,

is concerned, and has 1 too heavy or too resinous time of about three hours. The4 duid state similar in appearance and effectivenass to the fresh fredoil" complex, the virtues o! which have been referred to earlier in this specincation.4 Under the iniluence ot hydrogenation catalysts. and particularlythose of the rugged type, the reactivation is more rapid and more complete than might otherwise be the case, and extremely viscous or tarry sludge can be easily and quickly regenerated tol a iight colored low viscosity aluminum halide hydrocarbon complex. Moreover, under the conditions herein set forth, there is no appreciable loss oi material as free aluminum or aluminum oxide. as occurs in destructive hydrogenation, coking, distillation, etc.

Although I have shown one embodiment of my invention, it should be understood that this is by way of illustration and not by way of limita-V tion. Various details, such as pumps, automatic controls, heat exchangers, etc., have been omitted for the sake of simplicity and will be readily supplied by one skilled in the art my invention commercially. Y

I claim: 1. A process for the recovery of a catalytlcally active aluminum halide-hydrocarbon complex from a comparatively inactive aluminum halidewishing to practice v hydrocarbon sludgev formed during the conversion ako tion catalyst other of hydrocarbons in the presence of an aluminum halide catalyst which comprises treating said aluminum halide-hydrocarbon sludge with hyin the presence of an activehydrogenation catalyst other aluminum halide which may be present in said sludge and in the substantial absence of other regenerating agents under conditions of temperature andpressure adapted to promote the restoration of said aluminum halide-hydrocarbon lsludge to a catalytically active tluid complex state.

2. A process for therecovery of a catalytically active aluminum, .halide-hydrocarbon complex from a comparatively inactive aluminum halidehydrocarbon sludge formed during the conversion of hydrocarbons in the presence of an aluminum halide catalyst which comprises treating said aluminum lhalide-hydrocarbon drogen in the presence of an active hydrogenathan any catalytlcally active aluminum halidewhich may be present in said sludge and in the substantialabsence of other regenerating agents at a temperature' within the approximate range of. from 200 to 500 F. and under pressure adapted to promote the restoration/of said aluminum halide-hydrocarbon sludge to a catalytlcally active fluid complex state.

3. A process for the recovery of a catalytlcally active aluminum halide-hydrocarbon complex from a comparatively inactive aluminum halidehydrocarbon sludge formed during the conversion of hydrocarbons in the presence of an aluminum halide catalyst which comprises treating said aluminum halide-hydrocarbon sludge with hydrogen in the presence of an active hydrogenation catalyst other than any catalytlcally active from a comparatively inactive aluminum halidethan any catalytlcally activey sludge with hyof from 40 to 400 atmospheres l said aluminum minum halide catalyst which comprises treating halide-hydrocarbon sludge with hydrogen in the presence of an active hydrogena- `tion catalyst selected from the group comprising the oxides and-sulides of the heavy metals of the sixth group of the periodic system under such conditions of temperature and pressure that there is no substantial vaporization oi' aluminum chloride but that there is a restoration o; said aluminum halide-hydrocarbon complex to a cata-V lytically active iluid state.

5. A process for the recovery of a catalytically active aluminum. halide-hydrocarbon complex from a comparatively inactivealuminum halidehydrocarbon sludge formed during the conversion of hydrocarbons in the presence of an aluminum halide catalyst which comprises treating said aluminum halide-hydrocarbon:sludge with hydrogen in the presence of an active hydrogenafrom the group comprising tion catalyst selected the oxides and sulfides of the heavy metals of the sixth group oi the periodic system at temperatures within the range of from about 200" F. to 500 F., at pressures within the range of from about 40 to 400 atmospheres whereby said aluminum halide-hydrocarbon sludge is converted f to a catalytically active fluid aluminum halidehydrocarbon complex.

aaaaaoa hydrocarbon sludge formed during the conversion of hydrocarbons in the presence loi'ian alu- 6. In a process including reacting a. hydrocarbon material with an aluminum halide-hydrocarbon complex wherein said complex becomes degraded and reduced in catalytic activity. the improvement comprising treating said degraded complex with hydrogen in the presence of an active hydrogenation catalyst other than any catalyticaliy active aluminum halide which may be present in said sludge and in the substantial absence of other regenerating agents under conditions whereby the catalytic activity of said complex is substantially restored.

7. In a process including reacting a hydrocarbon material with an aluminum halide-hydro carbon complex wherein said complex becomes degraded and reduced in catalytic activity, the improvement comprising separating said degraded catalytic complex from said hydrocarbon v material, treating said separated complex with hydrogen in the presence of an active hydrogenation catalyst other than any catalytically active aluminum halide which may be present in said sludge and in the substantial absence of other regenerating agents at a temperature within the approximate range of from 200 to 500 F. and a pressure within the approximate range of from 40 to 400 atmospheres.

JAMES M. PAGE. Ja. 

